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Acta Cryst. (2007). E63, m1514    [ doi:10.1107/S1600536807020533 ]

Tetraaquabis[(4-oxo-4H-pyridin-1-yl)acetato]manganese(II)

Z.-Y. Zhang, S. Gao, L.-H. Huo and J.-G. Zhao

Abstract top

In the title centrosymmetric mononuclear MnII complex, [Mn(C7H6NO3)2(H2O)4], the MnII ion, which lies on an inversion centre, has an octahedral geometry and is six-coordinated by two carbonyl O atoms from two (4-oxo-4H-pyridin-1-yl)acetate (4-OPA-) anions and four water molecules. The mononuclear units are linked into a two-dimensional network parallel to the (01\overline{1}) plane by O-H...O intermolecular hydrogen bonds. Adjacent networks are cross-linked via weak [pi]-[pi] stacking interactions between pyridine rings, with a centroid-centroid distance of 3.758 (3) Å

Comment top

(4-Oxo-4H-pyrindin-1-yl)acetic acid (4-OPA−), an important medical intermediate (Edwards et al., 1977), is a potential multidentate ligand with versatile binding ability. Recent studies in our laboratory have demontrated that the complexes containing 4-OPA− ligands exhibit two type structures: mononuclear in which the 4-OPA− ligands exist as counter anions (Gao et al., 2004; Zhang et al., 2004a,b; Zhao et al., 2004; Zhang et al., 2005) and polymer with the adjacent metal ions bridged by carbonyl and carboxylate groups of 4-OPA− ligand (Zhang et al., 2006).

As illustrated in Fig. 1, the title complex has a mononuclear structure, in which the (4-oxo-4H-pyridin-1-yl)acetate ligands are coordinated to the MnII atom through the carbonyl O atoms in a monodentate fashion. The MnII atom is located on an inversion center and is coordinated by two carbonyl O atoms and four water molecules, forming an octahedral coordination geometry. The Mn—Ocarbonyl bond distance is 2.1960 (11) Å, and the Mn—Ow distances are 2.1557 (14) and 2.1952 (12) Å.

The planes of the carboxylate group (O1/O2/C1/C2) and pyridine ring (N1/C3—C7) form a dihedral angle of 67.27 (9)°. The C—O bond lengths [O1—C1 = 1.2566 (18) Å and O2—C1 = 1.2366 (19) Å] suggest delocalization of π-electron density over the carboxylate group.

The coordinated water molecules form intermolecular O—H···O hydrogen bonds with uncoordinated carboxylate groups of adjacent molecules, connecting the mononuclear units into a two-dimensional network parallel to the (0 1 1) plane. The O···O distances of the hydrogen bonds lie in the range 2.6557 (17)–2.7677 (17) Å and the O—H···O angles range from 169.5 (19) to 178 (2)° (Table 1). The adjacent networks are cross-linked via weak π-π stacking interactions between the pyridine rings of the molecules at (x, y, z) and (1 − x, 1 − y, −z), with a centroid···centroid distance of 3.758 (3) Å (Fig. 2).

Related literature top

For general background, see: Edwards et al. (1977). Complexes with 4-OPA− exist as either mononuclear with the ligands as counter-anions (Gao et al., 2004; Zhang et al., 2004a,b; Zhao et al., 2004; Zhang et al., 2005) or as polymers with the metal ions bridged by the 4-OPA− ligands (Zhang et al., 2006).

Experimental top

The title complex was prepared by the addition of MnCl2·4H2O (3.96 g, 20 mmol) to a solution of (4-oxo-4H-pyridin-1-yl)acetic acid (5.84 g, 40 mmol) in H2O-DMF (1:1 v/v), and the pH was adjusted to 7 with 0.2 M NaOH solution. Colourless single crystals of (I) were obtained from the filtered solution, after slow evaporation at room temperature for a week. Analysis calculated for C14H20MnN2O10: C 38.99, H 4.67, N 6.49%; found: C 38.77, H 4.54, N 6.66%.

Refinement top

H atoms of water molecules were located in Fourier difference maps and refined with the restraints O—H = 0.85 (1) Å and H···H = 1.39 (1) Å, and with Uiso(H) = 1.5Ueq(O). C-bound H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å and Uiso(H) = 1.2Ueq(C), and were included in the refinement in the riding-model approximation.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of complex (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry code: (i) 1 − x, 1 − y, 1 − z.
[Figure 2] Fig. 2. The three-dimensional network of (I), viewed along the a axis. Dashed lines indicate O–H···O hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted. Cg1 and Cg2 represent the centroids of adjacent pyridine rings, as defined in the comment.
Tetraaquabis[(4-oxo-4H-pyridin-1-yl)acetato]manganese(II) top
Crystal data top
[Mn(C7H6NO3)2(H2O)4]Z = 1
Mr = 431.26F(000) = 223
Triclinic, P1Dx = 1.626 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.4191 (11) ÅCell parameters from 4131 reflections
b = 9.0498 (18) Åθ = 3.9–27.5°
c = 10.044 (2) ŵ = 0.81 mm−1
α = 108.16 (3)°T = 295 K
β = 99.32 (3)°Prism, colourless
γ = 103.38 (3)°0.36 × 0.28 × 0.18 mm
V = 440.5 (2) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1981 independent reflections
Radiation source: fine-focus sealed tube1844 reflections with I > 2σ(I)
graphiteRint = 0.014
Detector resolution: 10.000 pixels mm-1θmax = 27.5°, θmin = 3.9°
ω scansh = −6→7
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −11→11
Tmin = 0.760, Tmax = 0.868l = −13→13
4337 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0396P)2 + 0.1219P]
where P = (Fo2 + 2Fc2)/3
1981 reflections(Δ/σ)max = 0.001
136 parametersΔρmax = 0.33 e Å−3
6 restraintsΔρmin = −0.18 e Å−3
Crystal data top
[Mn(C7H6NO3)2(H2O)4]γ = 103.38 (3)°
Mr = 431.26V = 440.5 (2) Å3
Triclinic, P1Z = 1
a = 5.4191 (11) ÅMo Kα radiation
b = 9.0498 (18) ŵ = 0.81 mm−1
c = 10.044 (2) ÅT = 295 K
α = 108.16 (3)°0.36 × 0.28 × 0.18 mm
β = 99.32 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1981 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		1844 reflections with I > 2σ(I)
Tmin = 0.760, Tmax = 0.868Rint = 0.014
4337 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.071Δρmax = 0.33 e Å−3
S = 1.08Δρmin = −0.18 e Å−3
1981 reflectionsAbsolute structure: ?
136 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn10.50000.50000.50000.02410 (10)
O1W0.7476 (2)0.74902 (12)0.58032 (12)0.0342 (2)
H1W10.693 (3)0.8273 (18)0.624 (2)0.051*
H1W20.894 (3)0.789 (2)0.566 (2)0.051*
O10.2242 (2)−0.11738 (13)−0.45608 (12)0.0373 (3)
O2W0.79418 (19)0.41863 (13)0.61161 (11)0.0320 (2)
H2W10.775 (3)0.3193 (12)0.5618 (19)0.048*
H2W20.955 (2)0.4702 (19)0.634 (2)0.048*
O20.5889 (2)−0.00381 (14)−0.27545 (12)0.0402 (3)
O30.66629 (19)0.44717 (13)0.31126 (10)0.0324 (2)
N10.3688 (2)0.22273 (14)−0.12628 (12)0.0257 (2)
C10.3723 (3)−0.00777 (17)−0.34111 (14)0.0272 (3)
C20.2691 (3)0.13736 (17)−0.28357 (14)0.0298 (3)
H2A0.31940.2135−0.33130.036*
H2B0.07900.0990−0.30760.036*
C30.2162 (3)0.20104 (18)−0.03597 (15)0.0303 (3)
H30.04390.1340−0.07500.036*
C40.3070 (3)0.27423 (19)0.11032 (16)0.0317 (3)
H40.19550.25780.16910.038*
C50.5707 (3)0.37566 (17)0.17470 (15)0.0256 (3)
C60.7223 (3)0.39426 (18)0.07528 (15)0.0309 (3)
H60.89610.45940.11030.037*
C70.6192 (3)0.31899 (18)−0.07022 (16)0.0309 (3)
H70.72400.3343−0.13250.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.01991 (15)0.02699 (16)0.01976 (15)0.00453 (11)0.00473 (11)0.00294 (11)
O1W0.0286 (5)0.0281 (5)0.0383 (6)0.0039 (4)0.0135 (5)0.0030 (4)
O10.0295 (5)0.0329 (5)0.0332 (5)0.0051 (4)0.0037 (4)−0.0046 (4)
O2W0.0236 (5)0.0325 (5)0.0299 (5)0.0075 (4)0.0013 (4)0.0014 (4)
O20.0326 (6)0.0417 (6)0.0354 (6)0.0156 (5)0.0009 (5)0.0001 (5)
O30.0234 (5)0.0426 (6)0.0204 (5)0.0052 (4)0.0042 (4)0.0009 (4)
N10.0252 (5)0.0257 (5)0.0205 (5)0.0067 (4)0.0022 (4)0.0030 (4)
C10.0269 (7)0.0278 (7)0.0230 (6)0.0051 (5)0.0079 (5)0.0055 (5)
C20.0329 (7)0.0300 (7)0.0200 (6)0.0100 (6)0.0002 (5)0.0034 (5)
C30.0210 (6)0.0340 (7)0.0276 (7)0.0033 (5)0.0023 (5)0.0058 (6)
C40.0237 (6)0.0397 (8)0.0259 (7)0.0038 (6)0.0069 (5)0.0080 (6)
C50.0228 (6)0.0277 (6)0.0223 (6)0.0083 (5)0.0045 (5)0.0039 (5)
C60.0217 (6)0.0342 (7)0.0256 (7)0.0006 (5)0.0053 (5)0.0020 (6)
C70.0269 (7)0.0340 (7)0.0262 (7)0.0036 (5)0.0095 (6)0.0061 (6)
Geometric parameters (Å, °) top
Mn1—O1W2.1557 (14)O2W—H2W20.845 (9)
Mn1—O2W2.1952 (12)N1—C71.3481 (19)
Mn1—O32.1960 (11)N1—C31.3506 (19)
O1—C11.2566 (18)N1—C21.4677 (17)
O2—C11.2366 (19)C1—C21.531 (2)
O3—C51.2767 (17)C2—H2A0.97
C3—C41.359 (2)C2—H2B0.97
C6—C71.360 (2)C3—H30.93
Mn1—O1Wi2.1557 (14)C4—C51.423 (2)
Mn1—O2Wi2.1952 (12)C4—H40.93
Mn1—O3i2.1960 (11)C5—C61.417 (2)
O1W—H1W10.853 (9)C6—H60.93
O1W—H1W20.848 (9)C7—H70.93
O2W—H2W10.854 (9)
O1W—Mn1—O2W93.31 (5)C3—N1—C2120.87 (12)
O1W—Mn1—O2Wi86.69 (5)O2—C1—O1127.28 (14)
O1W—Mn1—O389.68 (5)O2—C1—C2118.63 (12)
O2W—Mn1—O389.39 (4)O1—C1—C2114.04 (13)
O1W—Mn1—O3i90.32 (5)N1—C2—H2A109.0
O2W—Mn1—O3i90.61 (4)C1—C2—H2A109.0
N1—C2—C1112.72 (12)N1—C2—H2B109.0
O1Wi—Mn1—O1W180C1—C2—H2B109.0
O1Wi—Mn1—O2W86.69 (5)H2A—C2—H2B107.8
O1Wi—Mn1—O2Wi93.31 (5)N1—C3—C4121.97 (13)
O2W—Mn1—O2Wi180N1—C3—H3119.0
O1Wi—Mn1—O390.32 (5)C4—C3—H3119.0
O2Wi—Mn1—O390.61 (4)C3—C4—C5120.86 (13)
O1Wi—Mn1—O3i89.68 (5)C3—C4—H4119.6
O2Wi—Mn1—O3i89.39 (4)C5—C4—H4119.6
O3—Mn1—O3i180.0O3—C5—C6121.59 (12)
Mn1—O1W—H1W1121.0 (13)O3—C5—C4123.50 (13)
Mn1—O1W—H1W2130.2 (12)C6—C5—C4114.91 (12)
H1W1—O1W—H1W2108.3 (13)C7—C6—C5121.46 (13)
Mn1—O2W—H2W1108.5 (13)C7—C6—H6119.3
Mn1—O2W—H2W2120.6 (14)C5—C6—H6119.3
H2W1—O2W—H2W2107.7 (13)N1—C7—C6121.54 (13)
C5—O3—Mn1134.77 (9)N1—C7—H7119.2
C7—N1—C3119.26 (12)C6—C7—H7119.2
C7—N1—C2119.81 (12)
O1Wi—Mn1—O3—C547.96 (14)N1—C3—C4—C5−1.0 (2)
O1W—Mn1—O3—C5−132.04 (14)Mn1—O3—C5—C6164.14 (11)
O2W—Mn1—O3—C5134.65 (14)Mn1—O3—C5—C4−15.0 (2)
O2Wi—Mn1—O3—C5−45.35 (14)C3—C4—C5—O3−179.92 (14)
C7—N1—C2—C174.23 (17)C3—C4—C5—C60.9 (2)
C3—N1—C2—C1−103.03 (15)O3—C5—C6—C7−179.46 (14)
O2—C1—C2—N1−28.52 (19)C4—C5—C6—C7−0.3 (2)
O1—C1—C2—N1153.79 (13)C3—N1—C7—C60.3 (2)
C7—N1—C3—C40.4 (2)C2—N1—C7—C6−177.01 (14)
C2—N1—C3—C4177.64 (14)C5—C6—C7—N1−0.3 (2)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2ii0.85 (1)1.82 (1)2.6674 (17)178 (2)
O1W—H1W2···O1iii0.85 (1)1.87 (1)2.7208 (17)177 (2)
O2W—H2W1···O1iv0.85 (1)1.81 (1)2.6557 (17)173 (2)
O2W—H2W2···O3v0.84 (1)1.93 (1)2.7677 (17)169 (2)
Symmetry codes: (ii) x, y+1, z+1; (iii) x+1, y+1, z+1; (iv) −x+1, −y, −z; (v) −x+2, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2i0.85 (1)1.82 (1)2.6674 (17)178 (2)
O1W—H1W2···O1ii0.85 (1)1.87 (1)2.7208 (17)177 (2)
O2W—H2W1···O1iii0.85 (1)1.81 (1)2.6557 (17)173 (2)
O2W—H2W2···O3iv0.84 (1)1.93 (1)2.7677 (17)169 (2)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z+1; (iii) −x+1, −y, −z; (iv) −x+2, −y+1, −z+1.
Acknowledgements top

We thank the Heilongjiang Province Natural Science Foundation (No. B200501), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (No. 1054 G036), Heilongjiang University, and Harbin Medical University for supporting this work.

references
References top

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